US9145476B2 - Plastic containers with gas barrier coating and optionally hydrophilic inside coating - Google Patents

Plastic containers with gas barrier coating and optionally hydrophilic inside coating Download PDF

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Publication number
US9145476B2
US9145476B2 US13/487,588 US201213487588A US9145476B2 US 9145476 B2 US9145476 B2 US 9145476B2 US 201213487588 A US201213487588 A US 201213487588A US 9145476 B2 US9145476 B2 US 9145476B2
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process according
plastic container
coating
polyvinyl
coating layer
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US20120306126A1 (en
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Robert Fuss
Norman James Gottlieb
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CONTAINER COOPERATION OF CANADA
Kuraray Europe GmbH
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Kuraray Europe GmbH
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    • C08J7/047—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/08—Coverings or external coatings
    • B65D23/0807—Coatings
    • B65D23/0814—Coatings characterised by the composition of the material
    • B65D23/0821—Coatings characterised by the composition of the material consisting mainly of polymeric materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3064—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062
    • B29C2949/3074—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062 said at least one component obtained by coating
    • B29C2949/3078—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062 said at least one component obtained by coating by spray coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/30—Preforms or parisons made of several components
    • B29C2949/3064—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062
    • B29C2949/3074—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062 said at least one component obtained by coating
    • B29C2949/308—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062 said at least one component obtained by coating by dip coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • This invention relates to plastic containers having a scratch and moisture resistant barrier coating against oxygen or carbon dioxide and optionally a hydrophilic inner coating to facilitate emptying. Furthermore, the invention relates to a process for manufacturing of such containers.
  • Plastic containers for food and beverages from polyethyleneterephthalate (PET), polypropylene (PP) or polyethylene (PE) are long known and are mostly produced in stretch blow molding processes.
  • WO 03/037969 A1, GB 879595, DE 10153210 and DE 10207592 A1 describe the use of polyvinyl alcohol as gas barrier on PET bottles with an additional top coat comprising polyvinyl butyral to improve the water resistance of the barrier coating.
  • Such multilayer coatings show a good barrier performance against oxygen and carbon dioxide, scratch resistance and are recyclable after mechanically destroying the top layer due the to the water solubility of the barrier coating.
  • plastic bottles for example used for soft drinks are produced by injection stretch blow molding from so called preforms.
  • the preform is expanded to more than 10 times of its original volume resulting in a significant thinning of any coating layered on the surface of the preform.
  • the prior art suggests several film building polymers for the top coating.
  • GB 2337470 A1 discloses a method for coating a PET preform for bottles with a barrier coating based on PVA and protection of the barrier coated preform by applying a second polymeric material.
  • second polymeric material polyester like PET and polycarbonates are suggested.
  • This publication describes furthermore chemical or physical pre-treatments of the surface of the substrate prior to application of the barrier coating.
  • WO 2004/089624 A similar technique is disclosed by WO 2004/089624, where containers for food or manufactured goods from PET or polyolefins are first coated with a blend of at least two polymers including PVA, polyamines, polyvinylimines, polyacrylic acids etc. and subsequently with a protective coating of polyurethanes, PVC or polyacrylates.
  • the substrate may be pre-treated by plasma, flames, chlorine, fluorine or chemical etching.
  • Top coating polyvinyl alcohol as quite polar polymer with the polymers as proposed by this publication will result in mechanically and chemically unstable layers.
  • plastic containers are used for end consumer products like food (ketchup, mayonnaise, jam) or personal care (shampoo, body lotion).
  • end consumer products like food (ketchup, mayonnaise, jam) or personal care (shampoo, body lotion).
  • the present invention relates to a process for producing a plastic container with a barrier coating comprising the steps a) applying at least one coating layer of a first polyvinyl acetal on at least a part of the plastic container; b) applying at least one coating layer of polyvinyl alcohol on the first polyvinyl acetal layer; c) applying at least one top coating layer of a second polyvinyl acetal on the polyvinyl alcohol layer.
  • FIG. 1 illustrates corona, electronic beam or plasma treatment of a preform for a bottle
  • FIG. 2 illustrates a pre-treated preform of a bottle after oxyfluorination
  • FIG. 3 illustrates the coating of a preform having a base coating by dipping into an aqueous solution of polyvinyl alcohol
  • FIG. 4 illustrates the coating of a preform with a base coating of polyvinyl acetal a) and a barrier coating of polyvinyl alcohol b) by dipping into a solution of polyvinyl acetal (step c);
  • FIG. 5 illustrates a flow sequence for a preform coating line
  • FIGS. 6 a - 6 d illustrate a stretch blow process in accordance with the invention; is shown by way of example in FIG. 6 .
  • step a the preform is first heated and then transferred into the mold (b). After stretching by force s and pre-blowing (step c), the bottle is finally blown in step d.
  • FIG. 7 shows a coated preform according to the invention (a) which can be stretched without damaging the coating (b).
  • the stretched preform of FIG. 7 can be converted into a stretched pre-blown coated preform as shown in FIG. 8 a , which is finally inflated (blown) to a coated bottle ( FIG. 8 b );
  • FIG. 7 a illustrates a coated preform according to the invention
  • FIG. 7 b illustrates a stretched form of the coated preform of FIG. 7 a
  • FIG. 8 a illustrates pre-blown coated preform obtained from the stretched preform of FIG. 7 b
  • FIG. 8 b illustrates an inflated (blown) coated bottle obtained from the pre-blown coated preform of FIG. 8 a ;
  • FIGS. 9 a and 9 b illustrates a comparison of preform and bottle plasma treatment and coating.
  • the surface energy of at least a part of the inside surface of the plastic container is increased in step d) by applying at least one inner hydrophilic coating layer.
  • the first layer of polyvinyl acetal provided in step a) serves as base coating for the subsequent added barrier coating of polyvinyl alcohol and the second (top) layer of polyvinyl acetal.
  • the first base coating of polyvinyl acetal has strong adherence to the plastic material of the container and provides support for the polyvinyl alcohol layer provided in step b) and the top coating layer of polyvinyl acetal provided in step c).
  • the barrier coating comprising the layers manufactured in steps a, b and c) can be applied on at least a part of the outside or the inside of the containers.
  • the barrier coating may be applied to at least a part of the outside and inside of the plastic container or a preform thereof.
  • the term “at least a part of the outside or the inside of the container” refers to any part of the container where the gas barrier of the plastic material shall be improved by the method of the invention.
  • the entire outer or inner surface of the container is coated.
  • only the parts of the container are coated which have a lower gas barrier as other parts. It is within the invention to coat only the lid of a container which has on other parts a sufficient low gas permeability.
  • containers form multilayer cardboard have a good gas barrier, but are closed with lids having a low gas barrier. To improve the overall gas barrier and the shelf life of the packed good, it is sufficient to provide the lid with a barrier coating of the present invention.
  • Polyvinyl alcohol reduces the gas permeability (especially O 2 and CO 2 ) of the substrate significantly, thereby improving the shelf-life of packed foods, soft drinks or beer.
  • the use of coating consisting only of polyvinyl alcohol (PVA) is limited because of its moisture sensitivity.
  • PVA polyvinyl alcohol
  • polyvinyl acetals are especial suitable as base and top coating for PVA layer since both polymers have a similar polymeric backbone and are compatible in a broad range of mixtures.
  • the plastic material may be coated untreated or optionally prior to step a) pre-treated by chemical roughening, oxyfluorination, corona, electron beam or flame treatment.
  • Pre-treatment can enhance the adherence of the layers to the substrate.
  • pre-treatment is an additional process step and the method of the invention provides in most cases mechanical stable coating layers which can be stretch-blown without cracks or delamination without pre-treatment.
  • the plastic material is optionally pre-treated or activated on the inside and/or outside by processes known in the art for such purposes.
  • the process of the invention may include mechanical roughening, corona, electronic beam, plasma treatment or flame treatment or oxyfluorination of at least a part of the surface of the plastic material.
  • FIG. 1 shows a typical preform for a bottle treated with corona, electronic beam or plasma.
  • Mechanical roughening can be achieved by a sandblast process, wherein the inside and/or outside surface of the container is provided with a roughness Rz of at least 100 ⁇ m, preferably 200 ⁇ m.
  • the pre-treatment or activation of at least a part of the surface of the plastic material results in an increase of the surface energy of the treated part of the plastic material of at least 25%, more preferably of at least 50%, based on the surface energy prior to treatment.
  • Untreated PET shows a surface energy of 30-45 mJ/m 2 . Accordingly, if the plastic material consists of PET, surface energy after pre-treatment should be at least 50 mJ/m 2 , preferable at least 55 mJ/m 2 and especially at least 60 mJ/m 2 , the upper range being 150 mJ/m 2 .
  • Untreated PP has a surface energy of 25-35 mJ/m 2 . Accordingly, if the plastic material consists of PP, surface energy after pre-treatment should be at least 45 mJ/m 2 , preferable at least 50 mJ/m 2 and especially at least 55 mJ/m 2 , the upper range being 150 mJ/m 2 .
  • the surface energy is measured according the manual of Accu Dyne TestTM Marker Pens.
  • Oxyfluorination is described in detail for example in WO2004/089624 or U.S. Pat. No. 5,900,321.
  • the pre-treatment by oxyfluorination according to this invention may be conducted by exposing at least a part of the surface of the plastic material to a fluorine-containing gas mixture containing 0.01% to 5% by volume fluorine and optionally inert gases like nitrogen or air, or an additional reactive species such as chlorine or oxygen.
  • Oxyfluorination for this invention may take place at a pressure of 10-10000 kPa, preferably 100-5000 kPa at a temperature of 10-90° C. with a time of exposure of 1 to 60 minutes.
  • FIG. 2 shows a pre-treated preform of a bottle, for example after Oxyfluorination.
  • “f” in FIG. 2 stands for the pre-treated/oxyfluorinated sites on the preform.
  • the preform may be pre-treated on the inside (i.e. the side of the container which will be in contact with the packed goods) and/or on the outside. Preferable, the preform is pre-treated only on the outside.
  • the first (base) layer of polyvinyl acetal is applied to the container.
  • polyvinyl acetal as the reaction product of polyvinyl alcohol with one or more aldehydes is used.
  • Suitable polyvinyl acetals are selected from the group consisting of polyvinyl butyral, polyvinyl acetyl-co-butyral and crosslinked polyvinyl butyral.
  • the acetalization degree of the polyvinyl acetals should be between 70 and 90 mol %, the polyvinyl alcohol content between 8 and 30 mol %.
  • the polyvinyl acetal is applied on the surface of the container and/or the polyvinyl alcohol layer as solution in an organic solvent, for example as solution in methyl ethyl ketone (MEK), methanol, acetone or ethanol for example by dip-coating, flowing or spraying.
  • MEK methyl ethyl ketone
  • the concentration of the coating solution is preferable between 5 and 25% by Weight.
  • the base layer from polyvinyl acetal thus applied may have a thickness of 0.01 to 5 ⁇ m.
  • Superfluous coating material may be removed by spinning of the plastic material.
  • the coating is dried at room temperature for 4-8 hours (overnight) or at elevated temperature in an oven with temperatures between 30 and 60° C. for 0.5 to 2 hours.
  • fast drying/curing is obtained in 15-30 sec.
  • the plastic material is coated with polyvinyl alcohol as barrier coating on the first layer of polyvinyl acetal.
  • the polyvinyl alcohol has a degree of saponification/hydrolization of at least 90%, preferable of at least 98%.
  • the PVA layer does not contain a plasticizer except some traces of moisture originating from the coating process.
  • the coating layer from polyvinyl alcohol may have a thickness of 0.01 to 5 ⁇ m.
  • the polyvinyl alcohol is applied as aqueous solution, for example by dip-coating, flowing or spraying.
  • the concentration of the coating solution is preferable between 5 and 25% by weight.
  • FIG. 3 shows the coating of a preform having a base coating by dipping into an aqueous solution of polyvinyl alcohol.
  • superfluous coating material may be removed by spinning of the plastic material.
  • the barrier-coated plastic material is dried to remove essential all water at ambient temperature of to 90° C., preferable 10-50° C. optionally at reduced pressure and then subjected to the protective top-coating with the second polyvinyl acetal.
  • First and second polyvinyl acetals may be different or identical polymers.
  • the process of coating and drying of the first and second layer of polyvinyl acetal may be different or identical. In order to reduce the complexity of the process it is preferred to utilize identical polyvinyl acetals and methods for both steps a) and c).
  • FIG. 4 shows the coating of a preform with a base coating of polyvinyl acetal a) and a barrier coating of polyvinyl alcohol b) by dipping into a solution of polyvinyl acetal (step c).
  • the barrier coating of steps a, b) and c) can be applied on at least a part of the outside or the inside of the plastic container. It is furthermore possible to apply the barrier coating of steps a, b) and c) on at least a part of the inside and at least a part of the outside of the plastic container.
  • the inner hydrophilic layer according to step d) is applied on at least a part of the inner surface of the container thereby increasing the surface energy of the inside of the container.
  • the layer can be applied on a pre-treated or an untreated surface. Suitable coating materials are for example vegetable fats or oils, glycerin esters, polyvinyl alcohol, polyvinyl acetal, but any substance which increases the surface energy of the inner surface of the container by the values mentioned for the pre-treatment can be used.
  • FIG. 5 shows a flow sequence for a preform coating line, where the coating steps a), b) are conducted by dipping the optionally pre-treated preform into solutions of polyvinyl alcohol and polyvinyl acetal with subsequent drying stations. Step c) is performed in the coating and drying station of step a). The preforms are transferred between the coating and drying station via transfer stations with appropriate machinery.
  • dyes or pigments are for example SiO 2 , Al 2 O 2 , or TiO 2 , as dyes “Rhenol”-type dyes from Clariant can be used.
  • concentration of dyes or pigments in each layer can range from 0.01 to 5 Wght %, based on the polymer.
  • the plastic material may be final shaped into a container by a blow-forming process a blowing process like stretch blowing or injection stretch blow molding.
  • the optional step d) may be performed prior or after the blowing process.
  • the plastic material to be coated with the process of the invention may comprise or consist of polymers selected from the group PET, PP, PE (polyethylene) and COC (cyclic olefin copolymer.
  • the plastic material may have any two or three dimensional shape like film or a container or a part of a container.
  • the coating may also be applied on a first shaped body (preform) which is then formed into the container.
  • Preform as used in this application is not limited to any shaped body, especially not to preforms of a bottle and may characterize any first shaped body which is used to produce the final container by another shaping process.
  • FIG. 1 shows a typical preform for a bottle.
  • Yet another object of the invention is a process to manufacture a container by subjecting a optionally pre-treated preform of the container, to a process comprising the already described coating steps a, b, c and optionally d) and subsequently shaping the preform into the final shape of the container.
  • shaping the preform is performed by a blowing process like stretch blowing or injection stretch blow molding.
  • FIG. 6 A stretch blow process for the invention is shown by way of example in FIG. 6 .
  • step a the preform is first heated and then transferred into the mold (b). After stretching by force s and pre-blowing (step c), the bottle is finally blown in step d.
  • FIG. 7 shows a coated preform according to the invention (a) which can be stretched without damaging the coating (b).
  • the stretched preform of FIG. 7 can be converted into a stretched pre-blown coated preform as shown in FIG. 8 a , which is finally inflated (blown) to a coated bottle ( FIG. 8 b )
  • the coating according to the invention may be applied to the outside or the inside or both sides of the container.
  • the containers coated by the process of the invention may be used for food, or beverages, drugs, spices, coffee, tea or chemicals.
  • the container may have a shape selected from the group consisting of capsules, blister packages, sachets, envelopes, jerry cans, bottles, jars and lids thereof.
  • FIG. 9 shows a comparison of preform and bottle plasma treatment and coating. Smooth non-obstructed preform shapes allow good access for surface treatment and uniform coating ( FIG. 9 a ). Side bottle grooves, curved-in bottom and side panels are difficult to reach areas for plasma surface treatment, easy to melt and result in coating uneven distribution with accumulation in the grooves and panel corners ( FIG. 9 b ).
  • a vessel of pressurized treatment gas was first prepared by pulling a strong vacuum ( ⁇ 1 torr) on a clean, dry steel pressure cylinder that had been passivated for fluorine service. To this was added 20% (by volume) of F 2 in nitrogen until a gauge pressure of 1061 kPa (154 psi) was achieved. Then dry, oil-free compressed air was added until the vessel achieved a gauge pressure of 3.4 MPa (500 psi). This cylinder was laid horizontally on a roller device and rolled for 48 hours to mix the gases to homogeneity.
  • Fluorooxidation was performed batch-wise in a steel vessel with an internal volume of 56 l (2 ft 3 ). Polypropylene containers were placed on a wire rack in the treatment vessel at ambient temperature, and the vessel door was closed and sealed. Using a vacuum pump, air was evacuated from the treatment vessel until a pressure of 5 torr was achieved. The pressurized treatment gas described above was admitted until an absolute pressure of 760 torr was achieved.
  • the polypropylene containers were left in the reactor with the fluorine gas mixture for 20 minutes.
  • the gases in the reactor were then removed by a vacuum pump that exhausted through a caustic scrubber.
  • the evacuated reactor was filled with dry, oil-free air to 765 torr and then evacuated to 5 torr. This purging step was performed ten times.
  • the reactor was again filled with dry, clean air, the door was opened, and the treated polypropylene containers were removed.
  • the surface energy of the polypropylene containers before fluorooxidizing was 30-34 mJ/m 2 , after pre-treatment the surface energy was found to be 52-56 mJ/m 2 (dynes/cm). Surface energy was measured with Accu Dyne TestTM Marker Pens.
  • a vessel of pressurized treatment gas was first prepared by pulling a strong vacuum ( ⁇ 1 torr) on a clean, dry steel pressure cylinder that had been passivated for fluorine service. To this was added 20% (by volume) of F 2 in nitrogen until a gauge pressure of 703 kPa (103 psi) was achieved. Then dry, oil-free compressed air was added until the vessel achieved a gauge pressure of 3.4 MPa (500 psi). This cylinder was then laid horizontally on a roller device and rolled for 48 hours to mix the gases to homogeneity. Fluorooxidation was performed batch-wise in a steel vessel with an internal volume of 56 l (2 ft 3 ).
  • PET containers were placed on a wire rack in the treatment vessel at ambient temperature.
  • the vessel door was closed and sealed.
  • air is evacuated from the treatment vessel until a pressure of 5 torr is achieved.
  • the pressurized treatment gas described above was admitted into the reaction vessel until an absolute pressure of 765 torr was achieved.
  • the PET containers were left in the reactor with the fluorine gas mixture for 15 minutes.
  • the gases in the reactor were removed by a vacuum pump that exhausted through a caustic scrubber.
  • the evacuated reactor was filled with dry, oil-free air to 760 torr and then evacuated to 5 torr. This purging step was performed ten times.
  • the reactor was again filled with dry, clean air, the door was opened, and the treated PET containers were removed.
  • the surface energy of the PET containers before fluorooxidizing was 36-40 mJ/m 2 , after pre-treatment the surface energy was found to be 56-60 mJ/m 2 (dynes/cm). Surface energy was measured with Accu Dyne TestTM Marker Pens.
  • Preforms for 500 ml bottles from PP and PET were used either untreated or pre-treated as described.
  • PVOH polyvinyl butyral
  • a 10 Wght % aqueous solution of MOWIOL 28-99 (PVA with a degree of saponification 99%) from Kuraray Europe GmbH was prepared and coated by dipping the preforms provided with the base coat into the solution. Excess coating liquid was removed by spinning and the coated preforms were left to dry overnight at room temperature.
  • a 10 Wght % ethanolic solution of MOWITAL SB 30HH as polyvinyl butyral (PVB) with a PVOH content of 18-21 mol % and a polyvinyl acetate content of 1-4 mol % was prepared and coated by dipping the preforms already coated in steps a) and b) into the solution. Excess coating liquid was removed by spinning and the coated preforms were left to dry overnight at room temperature.
  • the thus coated preforms were blown on a usual Stretch Blow Molding machine used to blow uncoated preforms from the respective substrate materials with substantial the same parameters for the shaping process as for PP or PET.
  • the following table shows the oxygen permeability results of coated bottles according to the invention as compared to uncoated bottles, as measured with a MoCon test equipment.
  • cc/pkg/day stands for loss of cubic centimeter gas per day per package
  • the bottles and the coating were mechanical stable against usual wear (for example fingernail scratch) and humidity (for example remove a water-filled bottle from the refrigerator). If the preform was not coated with the base coat a), oxygen permeability results were lower due to pinholes and/or cracks occurring in the coating after blowing. Furthermore, the coating can be removed by fingernail scratching and is then sensitive to moisture.
  • Table 1 shows that preforms coated without first polyvinylacetal base layer have an unsatisfactory mechanical performance. Accordingly, this preforms can not be shaped into the final container by a blowing process without delamination (Table 2).
  • preform coatings with a polyvinylacetal base layer i.e. according to the invention have an excellent mechanical behavior.
  • Table 4 shows that preforms coated with the method of the invention can be blown into bottles (i.e. shaped) with only minor delamination of the coating.
  • PET preforms 98 2 100 PET inflated containers 97 3 100 PET injection molded containers with 97 3 100 smooth surface PET injection molded containers with 95 5 100 rough surface PP preforms 97 3 100 PP inflated containers 96 4 100 PP injection molded containers with 96 4 100 smooth surface PP injection molded containers with 94 6 100 rough surface

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
US13/487,588 2011-06-06 2012-06-04 Plastic containers with gas barrier coating and optionally hydrophilic inside coating Expired - Fee Related US9145476B2 (en)

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EP11168859 2011-06-06
EP11168859.4A EP2532600B1 (en) 2011-06-06 2011-06-06 Plastic containers with gas barrier coating and optionally hydrophilic inside coating
EP11168859.4 2011-06-06

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EP3792035A4 (en) * 2018-05-10 2022-01-26 Suntory Holdings Limited Plastic bottle preform and method for production thereof

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US8057733B2 (en) 2007-12-21 2011-11-15 Silgan Plastics Corporation Dosing bottle and method
JP6037879B2 (ja) * 2013-02-13 2016-12-07 サントリーホールディングス株式会社 ガスバリアコーティングを有するプラスチックボトル用プリフォーム
JP6033108B2 (ja) * 2013-02-13 2016-11-30 サントリーホールディングス株式会社 バリアコーティング樹脂積層体及び該積層体を有するプラスチック容器
US9073294B2 (en) 2013-06-04 2015-07-07 Monosol, Llc Method for sealing a water-soluble film by applying a sealing solution
EP2824133A1 (en) * 2013-07-12 2015-01-14 Kuraray Europe GmbH Process of coating plastic containers with gas barrier coating to achieve improved moisture resistivity
BE1023737B1 (nl) 2013-09-13 2017-07-06 Resilux Werkwijze voor het vervaardigen van een gecoate voorvorm en behouder
JP2015199012A (ja) * 2014-04-04 2015-11-12 サントリーホールディングス株式会社 プリフォームコーティング装置、プリフォームの製造方法及びプラスチックボトルの製造方法
USD758526S1 (en) * 2014-07-24 2016-06-07 Jeffrey James Quail Compressed gas cartridge
JP6413571B2 (ja) * 2014-09-30 2018-10-31 大日本印刷株式会社 複合容器の製造方法、複合容器の充填方法および複合容器の充填装置
CN108025330B (zh) 2015-09-30 2021-07-20 三得利控股株式会社 预塑件涂敷装置及预塑件涂敷方法
WO2017072040A1 (en) 2015-10-27 2017-05-04 Kuraray Europe Gmbh Plastic containers with gas barrier coating having an inside thread for improved moisture resistance
CN109563292B (zh) 2016-07-18 2021-10-08 联合利华知识产权控股有限公司 一种改进容器分配特性的方法
US11453027B2 (en) 2017-12-25 2022-09-27 Suntory Holdings Limited Preform coating device
WO2019131686A1 (ja) 2017-12-25 2019-07-04 サントリーホールディングス株式会社 プリフォームコーティング装置
EP3733302A4 (en) 2017-12-25 2021-09-01 Suntory Holdings Limited PREFORM COATING DEVICE
JP7016890B2 (ja) 2017-12-25 2022-02-07 サントリーホールディングス株式会社 プリフォームコーティング装置
CN112074391A (zh) 2018-05-10 2020-12-11 三得利控股株式会社 塑料瓶用预塑形坯的涂布方法
NL2024298B1 (en) * 2019-11-22 2021-08-18 Heineken Supply Chain Bv Container with a coating layer
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WO2021156908A1 (ja) * 2020-02-03 2021-08-12 東洋製罐グループホールディングス株式会社 二重構造体
JP7115515B2 (ja) * 2020-06-19 2022-08-09 大日本印刷株式会社 プリフォーム及びボトル

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US9227381B2 (en) * 2010-10-06 2016-01-05 Toray Plastics (America), Inc. Multilayer barrier film having coating composition with organic particles
EP3792035A4 (en) * 2018-05-10 2022-01-26 Suntory Holdings Limited Plastic bottle preform and method for production thereof

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EP2532600A1 (en) 2012-12-12
US20120306126A1 (en) 2012-12-06
JP5680021B2 (ja) 2015-03-04
EP2532600B1 (en) 2020-01-22

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